US1639724A - Cecil john turrell cronshaw and william johnson smith nattnton - Google Patents
Cecil john turrell cronshaw and william johnson smith nattnton Download PDFInfo
- Publication number
- US1639724A US1639724A US1639724DA US1639724A US 1639724 A US1639724 A US 1639724A US 1639724D A US1639724D A US 1639724DA US 1639724 A US1639724 A US 1639724A
- Authority
- US
- United States
- Prior art keywords
- cronshaw
- cecil
- cyanogen
- john
- turrell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- ZPUCINDJVBIVPJ-LJISPDSOSA-N cocaine Chemical compound O([C@H]1C[C@@H]2CC[C@@H](N2C)[C@H]1C(=O)OC)C(=O)C1=CC=CC=C1 ZPUCINDJVBIVPJ-LJISPDSOSA-N 0.000 title 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 16
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 6
- ATDGTVJJHBUTRL-UHFFFAOYSA-N cyanogen bromide Chemical compound BrC#N ATDGTVJJHBUTRL-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 150000001555 benzenes Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- -1 cyanogen halide Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000000266 injurious effect Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000004992 toluidines Chemical class 0.000 description 2
- JZUFKLXOESDKRF-UHFFFAOYSA-N Chlorothiazide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC2=C1NCNS2(=O)=O JZUFKLXOESDKRF-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- IFXGUZKGCKIMQN-UHFFFAOYSA-N oxalonitrile;hydrate Chemical compound O.N#CC#N IFXGUZKGCKIMQN-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Inorganic materials [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/08—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of substituted guanidines
Definitions
- PROCESS FOR THE MANUFACTURE OF DIARYLGUANIDINES.
- the present invention avails itself of this known reaction between aniline or its homologues and cyanogen chloride or cyanogen bromide, but We have discovered conditions under which said reactions can be carried out on a manufacturlng scale without undue danger.
- cyanogen halide presence of water although water is not sub stantially a solvent for the cyanogen-chloride and bromide, but in our method of workmg, the water does not exert an injurious effect, but it helps in the regulation of the temperature, which is important, and substantially quantitative yields are obtained.
- Cyanogen bromide can be used in the same way as the cyanogen chloride above described and being much less volatile than the chloride, its poisonous action is not so dangerous, and it is more easily handled and maintained in the liquid condition. Further, there is the advantage that the production of the cyanogen bromide and its reaction on analine or the like can be effected in the same vessel. It is not neces sary to produce it elsewhere, purify it and then transfer it to the reaction vessel with the incident danger of handling. The pres ence of sodium or potassium bromide, the byproducts formed in making cyanogen bromide from solutions of potassium or sodium cyanide with bromine, is not injurious in the reaction of the present invention. For
- diphenylguanidine the process which comprises treating aniline with liquid cyanogen-chloride in the presence of water with cooling and violent agitation, and subsequently condensing the guanidine by raising the temperature to 90 C.
- diphenylguanidine the process which comprises treating aniline with a cyanogen halide in the liquid state and in the presence of water, with cooling and violent agitation and subsequently condensing the cyan-anilide so obtained to form diphenylguanidine by raising the temperature to 8085 C.
- diarylguanidines In the manufacture of diarylguanidines the process which comprises treating a mono-amine of the benzene series with a liquid cyanogen-chloride in the presence of water and condensing heating the cyanb V arylide so obtained to f brin a diarylguanidine.
- diarylguanidines which comprises treating a 1nonoamine of the benzene series with a liquid cyanogen halide in the presence of Water and condensing by heating the cyan-.arylide soobtained to form a diarylguanidine.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Aug. 23, 1927. I
UNITEDSTATES PATENT OFFICE. a
CECIL JOHN 'IDU'BJRLELL CRONSHAW AND WILLIAM JOHNSON SMITH-NAUNTON, OF MANCHESTER, ENGLfAND, -ASSIGNORS TO BRITISH DY ESTUFFS CORPORATION LIM- ITED, OF MANCHESTER,-ENGLAND. 1 i
PROCESS. FOR THE MANUFACTURE OF DIARYLGUANIDINES.
Io Drawing. Application, filed J'une" 28 1926, Serial No. 119,266, and in Great Britain July 4, 1925.
' 'Diphenylguanidine has recently been manufactured in considerable quantities as an accelerator, for use in the vulcanization The manufacturing processes completely different laboratory process for the manufacture ,of this body has been known since 1848. This process consists in the treatment of aniline with cyanogen chloride, dry vapors of cyanogen chloride be ing aspirated through liquid aniline, with condensation of the cyan-anilide obtained to form diphenylguanidine; this being isolated in suitable ways from-the more or less resinous mixture of products of reaction. The first description of this method was by Hoffmann in a paper read to the Chemical Society in June, 1848 (see the Quarterly Journal of the Chemical Society of the years 1849 and 1850, also Annalen der Chemie und Pharmacie (1848), vol. 67, page 129, and also Cahours and Cloez Anna-1e11, (185 1), vol. 90, page 93). The processes described in these references can no doubt be readily carried out, using proper precautions, in the laboratory, but they are not suitable for the manufacture of the diarylguanidines on any large scale. It is not practicable on a large scale to pass vapors of cyanogen chloride or of cyanogen bromide through aniline, toluidine or the like. The reaction is so violent as to be almost explosive and is particularly dangerous in view of the poisonous nature of the cyanogen compounds employed. Further, in the said descriptions it is repeatedly recommended that dry, water-free material should be used. The presence of water is stated to exert a deterrent efiect upon the condensation, giving low yields ofthe desired base, amongst other reasons because of the polymerization of the cyanogen chloride to cyanuric chloride. This View we have found to be incorrect. Water is not harmful and, on the other hand, the presence of liquid water is advantageous as aiding in the regulation of temperature and moderating the violence of the reaction. Polymerization of simple cyanogen chloride tocyanuric chloride is likewise of no detriment.
The present invention avails itself of this known reaction between aniline or its homologues and cyanogen chloride or cyanogen bromide, but We have discovered conditions under which said reactions can be carried out on a manufacturlng scale without undue danger. In particular the cyanogen halide presence of water although water is not sub stantially a solvent for the cyanogen-chloride and bromide, but in our method of workmg, the water does not exert an injurious effect, but it helps in the regulation of the temperature, which is important, and substantially quantitative yields are obtained.
Another feature of our process is that, as
stated, we do not pass vapour of cyanogen" chloride or of bromide through anilineor the like but on the contrary we run the aniline (for instance) slowly into a cold, violently agitated mixture of liquid cyanogen chloride and Water. The stirring is contmued whilst keeping the mixture cool till the production of the insoluble cyan-anilide is complete; then the temperature is raised to about 90 C. for about 4 hours, when a clear-solution of diphenylguanidine hydrochlor de is obtained. On running this clear solution into hot caustic soda solution, diphenylguanidine of high purity in substantially theoretical quantity is obtained.
It will be readily understood that instead of aniline, toluidine or other mono-amines of the benzene series can be used.
Cyanogen bromide can be used in the same way as the cyanogen chloride above described and being much less volatile than the chloride, its poisonous action is not so dangerous, and it is more easily handled and maintained in the liquid condition. Further, there is the advantage that the production of the cyanogen bromide and its reaction on analine or the like can be effected in the same vessel. It is not neces sary to produce it elsewhere, purify it and then transfer it to the reaction vessel with the incident danger of handling. The pres ence of sodium or potassium bromide, the byproducts formed in making cyanogen bromide from solutions of potassium or sodium cyanide with bromine, is not injurious in the reaction of the present invention. For
mixtureshould have a faintyellow colour due toithe presence of a little bromine. Whilst still maintaining thorough cooling "conditions, the theoretical quantity of anicyan-aniline so obtained to form diphenylline or the like is run gradually into the violently stirred mixture and the stirring continued until the formation of cyan-anilide is observed; then the temperature 'raisedto 80-85 C. for about 8 hours or more, and the resulting clear solution is run into hot caustic soda solution.
We'claim:
1. In the manufacture of diphenylguanidine, the process which comprises treating aniline with liquid cyanogen-chloride in the presence of water with cooling and violent agitation, and subsequently condensing the guanidine by raising the temperature to 90 C.
2. In the manufacture of diphenylguanidine the process Which comprises treating aniline with a cyanogen halide in the liquid state and in the presence of water, with cooling and violent agitation and subsequently condensing the cyan-anilide so obtained to form diphenylguanidine by raising the temperature to 8085 C.
3. In the manufacture of diarylguanidines the process which comprises treating a mono-amine of the benzene series with a liquid cyanogen-chloride in the presence of water and condensing heating the cyanb V arylide so obtained to f brin a diarylguanidine. y
'4 The process of making diarylguanidines which comprises treating a 1nonoamine of the benzene series with a liquid cyanogen halide in the presence of Water and condensing by heating the cyan-.arylide soobtained to form a diarylguanidine.
In testimony whereof We have hereunto affixed our signatures.
CECIL JOHN TURRELL CRONSHAW. WILLIAM JOHNSON SMITH NAUNTON.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1639724A true US1639724A (en) | 1927-08-23 |
Family
ID=3413205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US1639724D Expired - Lifetime US1639724A (en) | Cecil john turrell cronshaw and william johnson smith nattnton |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US1639724A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4542240A (en) * | 1980-02-28 | 1985-09-17 | Degussa Aktiengesellschaft | Process for the production of guanidine hydrochloride |
-
0
- US US1639724D patent/US1639724A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4542240A (en) * | 1980-02-28 | 1985-09-17 | Degussa Aktiengesellschaft | Process for the production of guanidine hydrochloride |
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